CN111299589A - Corrosion-resistant steel powder, feeding material and process for preparing corrosion-resistant steel complex parts - Google Patents
Corrosion-resistant steel powder, feeding material and process for preparing corrosion-resistant steel complex parts Download PDFInfo
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B22F3/10—Sintering only
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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Abstract
The invention relates to corrosion-resistant steel powder, a feeding material and a process for preparing a corrosion-resistant steel complex part, wherein the corrosion-resistant steel powder comprises the following components in percentage by mass: c is less than 0.5 percent, Cr: 6-10%, Ni: 4-8%, Mo: 1-3%, Co: 12-16%, Si less than 0.5%, Mn less than 0.5%, and the balance Fe. Wherein the corrosion-resistant steel feed comprises uniformly mixed corrosion-resistant steel powder and a binder; the preparation process comprises the following steps: s1, preparing the ultrahigh-strength steel feed; s2, molding: obtaining a molding blank by injection molding or dry pressing molding; s3, degreasing: degreasing the formed blank to form a degreased blank; s4, sintering: and placing the degreased blank in a continuous sintering furnace, and sintering to obtain a sintered blank. The invention expands the preparation method of the ultrahigh-strength steel part by the powder forming technology, and the method can also be used for preparing complex parts which cannot be prepared by the traditional preparation method, especially complex miniature parts.
Description
Technical Field
The invention relates to the field of powder forming, in particular to corrosion-resistant steel powder, feeding and a process for preparing corrosion-resistant steel complex parts.
Background
The ultra-strong corrosion-resistant steel is used as a special metal material with excellent performance, high strength, high toughness, corrosion resistance and easiness in processing, forming and welding, is mainly used for key force-bearing components such as energy development, petrochemical industry and aircraft landing gears, main beams, turbine engine spindles, engine housings, force-bearing bolts and the like, is prepared by a traditional method for preparing ultra-strong corrosion-resistant steel parts by adopting a fusion casting method, and has low preparation efficiency, product size precision and complexity.
With the increasingly strict requirements of the consumer electronics industry on the mechanical properties of metal materials, particularly the high precision and complexity of the current folding mobile phone hinge, the hinge requires the characteristics of high strength, toughness, wear resistance, corrosion resistance and the like, so that the ultrahigh-strength corrosion-resistant steel becomes a preferred material for the part. However, the traditional preparation method of the ultrahigh-strength corrosion-resistant steel part cannot prepare complex parts, particularly micro parts and micro complex parts. In the products of the electronic industry, there are many complex parts, micro parts and micro complex parts, so that how to apply the ultra-high-strength corrosion-resistant steel to the preparation of the parts always exists.
Disclosure of Invention
A first object of the present invention is to provide a corrosion-resistant steel powder that can be used in a powder molding process and by which a high-performance product can be obtained.
The technical scheme for realizing the first purpose of the invention is as follows: the corrosion-resistant steel powder comprises the following components in percentage by mass: c is less than 0.5 percent, Cr: 6-10%, Ni: 4-8%, Mo: 1-3%, Co: 12-16%, Si less than 0.5%, Mn less than 0.5%, and the balance Fe.
The control of the content of the component (element) of the corrosion-resistant steel powder is particularly important for controlling the content of the component because it directly affects the influence of the product in the later stage. When the corrosion-resistant steel powder is researched and developed, a great deal of technical research is carried out, and the mutual influence of the contents of the elements is one of the difficulties of the invention. According to a number of studies, the mechanism is as follows:
c (carbon): is a basic element having the greatest influence on the properties of steel, and is an austenite forming element which is very effective in suppressing ferrite formation at high temperatures and increasing the solid solution strengthening of cold-work-induced martensite phase. The influence of different carbon contents on the performance of the steel is different according to the content of impurity elements in the steel and the difference of cooling conditions after rolling, and along with the increase of the carbon content in the steel, the hardness of the carbon steel in a hot rolling state is increased linearly, and the plasticity and the toughness are reduced.
Cr (chromium): the ferrite element is an element required for ensuring corrosion resistance, can improve the strength and hardness of steel, improves the high-temperature mechanical property and hardenability of the steel and enables the steel to have good corrosion resistance and oxidation resistance, but when the content of the ferrite element is higher, the ferrite phase is easier to form in a high-temperature region, and austenite elements (C, N, Mn, Ni and the like) are required to be added for elimination, but when the content of the austenite elements is excessive, the austenite phase is stabilized, and the martensite phase is not beneficial to be induced to form in cold machining, so the ferrite element is determined by comprehensive evaluation.
Ni (nickel): as an austenite element at high temperature and room temperature, the strength of the steel can be improved without remarkably reducing the toughness, the workability and weldability of the steel can be improved, the corrosion resistance of the steel can be improved, and the steel can resist not only acid, but also alkali and atmosphere corrosion. However, the addition of the above is disadvantageous in that the martensite phase is induced to form during cold working.
Mo (molybdenum): molybdenum and chromium are elements which form and stabilize ferrite and expand a ferrite phase region, and molybdenum has a ferrite forming ability equivalent to that of chromium and has a solid solution strengthening effect and a hydrogen corrosion resistance effect on ferrite. Molybdenum also promotes intermetallic phases in austenitic stainless steel, the addition of molybdenum has little influence on the room-temperature mechanical properties, but the high-temperature strength of the steel is improved along with the increase of the content of molybdenum, and the properties such as durability, creep deformation and the like are greatly improved, and the hardenability of the steel is improved.
Co (cobalt): cobalt, like nickel and manganese, forms a continuous solid solution with iron, and suppresses and retards the precipitation and aggregation of special carbides of other elements during tempering or use. Cobalt is a matrix of the reinforced steel, and improves the hardness and strength in the annealed or normalized carbon steel, but can cause the reduction of plasticity and impact toughness, obviously improves the heat strength and high-temperature hardness of special-purpose steel and alloy, and improves the comprehensive mechanical property of the maraging steel, so that the maraging steel has super-strong toughness. Cobalt, as a non-carbide forming element, reduces the solid solubility of Mo in martensite, thereby promoting the formation of Mo2C precipitate phase, promoting the complete transformation of austenite into martensite, and reducing the tendency of martensite to transform into reverse austenite.
Si (silicon): generally acts as a deoxidizing agent, increasing the strength of solid solutions in the steel and the degree of cold work hardening, which reduces the toughness and plasticity of the steel. Excessive addition of silicon deteriorates the weldability of the steel by hardening the strain-induced martensite phase and also hardening it by entering the austenite phase in a solid solution state to promote the increase in the strength after aging.
Mn (manganese): as an element for controlling the stability of an austenite phase, the hardenability of the steel can be improved, the obvious effect on improving the strength of low-carbon and medium-carbon pearlite steel is achieved, and meanwhile, the high-temperature instantaneous strength of the steel is improved, but the high-temperature instantaneous strength of the steel is not as good as that of Mo; in addition, Mn is not added in excess as in other austenite phases, which is disadvantageous in that martensite phase is induced to form during cold working.
Ti (titanium): the same as Mo and Cr, has solid solution strengthening effect, can make the internal structure of steel compact, refine crystal grains, reduce aging sensitivity and cold brittleness, and can improve welding performance. Ti is also a ferrite-forming element, and a large content (> 2%) of Ti tends to form a ferrite phase or other brittle phases, which lowers toughness.
It follows that a great deal of research is required to obtain the corrosion-resistant steel powder of the present invention.
The second purpose of the invention is to provide a corrosion-resistant steel feed which can be used for powder forming complex parts, and the corrosion-resistant steel feed can provide favorable conditions for obtaining high-performance ultrahigh-strength corrosion-resistant steel complex parts (especially miniature parts) at the later stage through strict element content control.
The technical scheme for realizing the second purpose of the invention is as follows: the corrosion-resistant steel feed comprises uniformly mixed corrosion-resistant steel powder and a binder; the optimum loading φ 2 of the corrosion-resistant steel powder is obtained as follows:
formula 1:
formula 2: phi 2 is 0.96 phi 1
In formula 1,. rhoZDenotes the tap density, rho, of the corrosion-resistant steel powderLRepresents the theoretical density of the corrosion-resistant steel powder, and phi 1 represents the loading capacity; in the formula 2,. phi.2 represents the optimum loading amount.
The binder comprises POM, a skeleton agent, a dispersant, a lubricant and a stabilizer.
Alternatively, the binder includes a dispersant and a lubricant.
The third purpose of the invention is to provide a preparation process for preparing the ultrahigh-strength corrosion-resistant steel complex part; since the Metal Powder Injection Molding (Metal Powder Injection Molding) technology is one of the most advantageous Molding technologies at present, it has advantages over other processing methods in solving the problems of difficult Metal cutting and processing, complexity of Molding Metal parts, mass production and production efficiency, and can manufacture high-reliability, high-strength, high-precision complex micro parts. The invention effectively solves the dilemma of preparing load parts, especially load micro parts by ultra-high-strength corrosion-resistant steel through the powder forming technology.
The technical scheme for realizing the third purpose of the invention is as follows: the preparation process for preparing the ultrahigh-strength corrosion-resistant steel complex part comprises the following steps:
s1, preparing the corrosion-resistant steel feed: uniformly mixing the corrosion-resistant steel powder and the binder in a feed preparation machine according to the optimal loading capacity to prepare a feed;
s2, molding: obtaining a molding blank by injection molding or dry pressing molding; when injection molding is adopted, the corrosion-resistant steel feed prepared in the step S1 is placed in a powder injection molding machine and injected into a mold cavity to form a molding blank; when dry pressing molding is adopted, the corrosion-resistant steel feed prepared in the step S1 is placed in a dry press machine, and is subjected to dry pressing to a mold cavity to form a molding blank;
s3, degreasing: degreasing the formed blank to form a degreased blank;
s4, sintering: and placing the degreased blank in a continuous sintering furnace, and sintering to obtain a sintered blank.
When the injection molding is adopted in the step S2, the corrosion-resistant steel feed prepared in the step S1 is placed in a powder injection molding machine, and is injected into a mold cavity under the conditions of 100-180 MPa of injection pressure and 150-200 ℃ of injection temperature to form a molding blank; when dry pressing is adopted, the corrosion-resistant steel feed prepared in the step S1 is placed in a dry press, and is subjected to dry pressing to a die cavity under the pressure of 10-20 Mpa, so that a forming blank is formed.
In the step S3, performing nitric acid catalytic degreasing on the molded blank formed by injection molding to form a degreased blank, wherein the flow rate of the nitric acid is 2-5 ml/min, the catalytic temperature is 80-120 ℃, and the degreasing time t is not less than (240+ 60H) min, wherein H is the maximum wall thickness of the complex part and the unit is mm; carrying out hot stripping on the formed blank formed by dry pressing to form a degreased blank; and the thermal desorption time t is more than or equal to (600+ 60H) min, wherein H is the maximum wall thickness of the complex part and is measured in mm.
In the step S4, the degreased blank is placed in a continuous sintering furnace and put in H2Sintering in the atmosphere to obtain a sintered blank; the sintering temperature T is controlled to be 1330-1380 ℃, and the heat preservation time is 2 hours.
Simultaneously, the method also comprises the following steps: the sintered compact is heat treated and/or shaped and/or machined and/or surface treated. Wherein the heat treatment comprises solution and cold treatment.
When injection molding is adopted, the binder comprises POM, a skeleton agent, a dispersing agent, a lubricating agent and a stabilizing agent.
When dry-pressing is used, the binder includes a dispersant and a lubricant.
The invention has the positive effects that: (1) in order to meet the performance requirements of ultrahigh-strength corrosion-resistant steel powder molding high-precision complex parts, the invention deeply researches the influence of the element content of the corrosion-resistant steel powder on the product performance, and obtains the high-performance ultrahigh-strength corrosion-resistant steel complex parts through strict element content control.
(2) The invention prepares the ultrahigh-strength corrosion-resistant steel part by using a powder forming process for the first time, and obtains the high-performance ultrahigh-strength corrosion-resistant steel complex part through a unique sintering process and a heat treatment process.
(3) The ultrahigh-strength corrosion-resistant steel complex part prepared by the method can be applied to 3C products, and has revolutionary innovation for promoting the expansion of a powder molding material system and the development of the consumer electronics industry.
Detailed Description
(example 1)
The corrosion-resistant steel powder comprises the following components in percentage by mass: c is less than 0.5 percent, Cr: 6-10%, Ni: 4-8%, Mo: 1-3%, Co: 12-16%, Si less than 0.5%, Mn less than 0.5%, and the balance Fe;
the corrosion-resistant steel feed comprises the corrosion-resistant steel powder and a binder which are uniformly mixed; the binder comprises POM, a skeleton agent, a dispersant, a lubricant and a stabilizer; the specific components of the binder are as follows:
the optimum loading φ 2 of the corrosion-resistant steel powder is obtained as follows:
formula 1:
formula 2: phi 2 is 0.96 phi 1
In formula 1,. rhoZShows the tap density of the corrosion-resistant steel powderDegree, rhoLRepresents the theoretical density of the corrosion-resistant steel powder, and phi 1 represents the loading capacity; in the formula 2,. phi.2 represents the optimum loading amount. According to the calculation, the optimum loading φ 2 was 61.2%.
The preparation process for preparing the ultrahigh-strength corrosion-resistant steel complex part comprises the following steps:
s1, preparing the corrosion-resistant steel feed: the corrosion-resistant steel powder is prepared by putting corrosion-resistant steel powder and a binder into a feeding preparation machine for mixing;
s2, molding: placing the corrosion-resistant steel feed prepared in the step S1 in a powder injection molding machine, and injecting the feed into a mold cavity to form a molding blank;
s3, degreasing: degreasing the formed blank to form a degreased blank;
s4, sintering: placing the degreased blank in a continuous sintering furnace, and sintering to obtain a sintered blank;
s5, heat treatment: heating the sintered blank to 1050 ℃, keeping the temperature for one hour, and then rapidly cooling; after the solution treatment, the steel is refrigerated to-80 ℃ and kept for 1 hour, then is heated to room temperature (CT), and then is heated to 490 ℃ and kept for 5 hours;
s6, shaping/machining: machining the sintered part to an optimal size according to the standard given by a customer;
s7, other post-processing method: and (6) surface treatment.
Step S2, placing the corrosion-resistant steel feed prepared in the step S1 in a powder injection molding machine, and injecting the feed into a mold cavity under the conditions of 100-180 MPa injection pressure and 150-200 ℃ injection temperature to form a molding blank;
and in the step S3, performing nitric acid catalytic degreasing on the molded blank to form a degreased blank, wherein the flow rate of the nitric acid is 2-5 ml/min, the catalytic temperature is 80-120 ℃, and the degreasing time t is not less than (240+ 60H) min, wherein H is the maximum wall thickness of the complex part and the unit is mm.
In the step S4, the degreased blank is placed in a continuous sintering furnace and is subjected to H2Sintering in the atmosphere to obtain a sintered blank; the sintering temperature T is controlled to be 1340-1370 ℃, and the holding time is 1.5 hours.
The test data for the parts prepared in this example are as follows:
(example 2)
The corrosion-resistant steel powder comprises the following components in percentage by mass: c is less than 0.5 percent, Cr: 6-10%, Ni: 4-8%, Mo: 1-3%, Co: 12-16%, Si less than 0.5%, Mn less than 0.5%, and the balance Fe.
The corrosion-resistant steel feed comprises the corrosion-resistant steel powder and a binder which are uniformly mixed, and the specific composition is as follows:
the optimum loading φ 2 of the corrosion-resistant steel powder is obtained as follows:
formula 1:
formula 2: phi 2 is 0.96 phi 1
In formula 1,. rhoZDenotes the tap density, rho, of the corrosion-resistant steel powderLRepresents the theoretical density of the corrosion-resistant steel powder, and phi 1 represents the loading capacity; in the formula 2,. phi.2 represents the optimum loading amount. According to the calculation, the optimum loading φ 2 was 61.2%.
The preparation process for preparing the ultrahigh-strength corrosion-resistant steel complex part comprises the following steps:
s1, preparing the corrosion-resistant steel feed: the corrosion-resistant steel powder is prepared by putting corrosion-resistant steel powder and a binder into a feeding preparation machine for mixing;
s2, molding: placing the corrosion-resistant steel feed prepared in the step S1 in a dry press, and dry-pressing the corrosion-resistant steel feed into a mold cavity of a mold to form a molding blank;
s3, degreasing: degreasing the formed blank to form a degreased blank;
s4, sintering: and placing the degreased blank in a continuous sintering furnace, and sintering to obtain a sintered blank.
S5, heat treatment: heating the sintered blank to 950 ℃, keeping the temperature for one hour, and then rapidly cooling; the part below 30cm can be quenched with a suitable liquid quenching agent, and the part above 30cm should be rapidly cooled in air. After the solution treatment, the steel is refrigerated to-80 ℃ and kept for 2 hours, then is heated to room temperature (CT), and then is heated to 580 ℃ and kept for 6 hours;
s6, shaping/machining, namely machining the sintered part to an optimal size according to the standard given by a customer;
s7, other post-processing method: and (6) surface treatment.
And step S2, placing the corrosion-resistant steel feed prepared in the step S1 in a dry press, and performing dry pressing at the pressure of 20Mpa into the cavity of the die to form a forming blank.
In the step S3, the molded blank is thermally stripped to form a degreased blank; and the thermal desorption time t is more than or equal to (600+ 60H) min, wherein H is the maximum wall thickness of the complex part and is measured in mm.
In the step S4, the degreased blank is placed in a continuous sintering furnace and is subjected to H2Sintering in the atmosphere to obtain a sintered blank; the sintering temperature T is controlled to be 1340-1370 ℃, and the holding time is 2 hours.
The test data for the parts prepared in this example are as follows:
the above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. The corrosion-resistant steel powder is characterized by comprising the following components in percentage by mass: c is less than 0.5 percent, Cr: 6-10%, Ni: 4-8%, Mo: 1-3%, Co: 12-16%, Si less than 0.5%, Mn less than 0.5%, and the balance Fe.
2. The corrosion-resistant steel feed is characterized in that: comprising uniformly mixing the corrosion-resistant steel powder of claim 1 and a binder; the optimum loading φ 2 of the corrosion-resistant steel powder is obtained as follows:
formula 1:
formula 2: phi 2 is 0.96 phi 1
In formula 1,. rhoZDenotes the tap density, rho, of the corrosion-resistant steel powderLRepresents the theoretical density of the corrosion-resistant steel powder, and phi 1 represents the loading capacity; in the formula 2,. phi.2 represents the optimum loading amount.
3. A corrosion resistant steel feedstock as set forth in claim 2 wherein: the binder comprises POM, a skeleton agent, a dispersing agent, a lubricant, a toughening agent and a stabilizing agent.
4. A corrosion resistant steel feedstock as set forth in claim 2 wherein: the binder includes a dispersant and a lubricant.
5. The preparation process of the corrosion-resistant steel complex part is characterized by comprising the following steps of:
s1, preparing a corrosion-resistant steel feed as claimed in claim 2;
s2, molding: obtaining a molding blank by injection molding or dry pressing molding; when injection molding is adopted, the corrosion-resistant steel feed prepared in the step S1 is placed in a powder injection molding machine and injected into a mold cavity to form a molding blank; when dry pressing molding is adopted, the corrosion-resistant steel feed prepared in the step S1 is placed in a dry press machine, and is subjected to dry pressing to a mold cavity to form a molding blank;
s3, degreasing: degreasing the formed blank to form a degreased blank;
s4, sintering: and placing the degreased blank in a continuous sintering furnace, and sintering to obtain a sintered blank.
6. The process for preparing the ultrahigh-strength corrosion-resistant steel complex part according to claim 5, wherein the process comprises the following steps: when the step S2 is adopted, the corrosion-resistant steel feed prepared in the step S1 is placed in a powder injection molding machine and is injected into a mold cavity under the conditions of 100-180 MPa injection pressure and 150-200 ℃ injection temperature to form a molding blank; when dry pressing is adopted, the corrosion-resistant steel feed prepared in the step S1 is placed in a dry press, and is subjected to dry pressing to a die cavity under the pressure of 10-20 Mpa, so that a forming blank is formed.
7. The process for preparing the ultrahigh-strength corrosion-resistant steel complex part according to claim 5, wherein the process comprises the following steps: in the step S3, performing nitric acid catalytic degreasing on the molded blank formed by injection molding to form a degreased blank, wherein the flow rate of the nitric acid is 2-5 ml/min, the catalytic temperature is 80-120 ℃, and the degreasing time t is more than or equal to (240+ 60H) min, wherein H is the maximum wall thickness of the complex part and the unit is mm; carrying out hot stripping on the formed blank formed by dry pressing to form a degreased blank; and the thermal desorption time t is more than or equal to (600+ 60H) min, wherein H is the maximum wall thickness of the complex part and is measured in mm.
8. The process for preparing the ultrahigh-strength corrosion-resistant steel complex part according to claim 5, wherein the process comprises the following steps: in the step S4, the degreased blank is placed in a continuous sintering furnace and is subjected to H2Sintering in the atmosphere to obtain a sintered blank; the sintering temperature T is controlled to be 1330-1380 ℃, and the heat preservation time is 2 hours.
9. The process for preparing the ultrahigh-strength corrosion-resistant steel complex part according to claim 5, wherein the process comprises the following steps: also comprises the following steps: the sintered compact is heat treated and/or shaped and/or machined and/or surface treated.
10. The process for preparing the ultrahigh-strength corrosion-resistant steel complex part according to claim 5, wherein the process comprises the following steps: when injection molding is employed, the binder includes POM, a backbone, a dispersant, a lubricant, a toughening agent, and a stabilizer.
11. The process for preparing the ultrahigh-strength corrosion-resistant steel complex part according to claim 5, wherein the process comprises the following steps: when dry-pressing is used, the binder includes a dispersant and a lubricant.
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